Gasoline compositions

ABSTRACT

GASOLINE COMPOSITIONS CONTAINING NORMALLY LIQUID NONAROMATIC OLEFIN HYDROCARBONS HAVING AN AVERAGE MOLECULAR WEIGHT OF FROM 350 TO ABOUT 1500; THE COMPPOSITION ARE CHARACTERIZED BY SUBSTANTIALLY REDUCING THE UNDERHEAD INTAKE VALVE DEPOSIT FORMATION WHEN USED AS FUELS IN A SPARK IGNITION, INTERNAL COMBUSTION ENGINE. PREFERRED OLEFIN HYDROCARBONS ARE THOSE PREPARED BY FRIEDEL-CRAFTS POLYMERIZATION OF A MIXTURE OF MONOOLEFINS WITH CARBON NUMBERS RANGING FROM ABOUT C12 AND HIGHER.

United States Patent O 1 3,749,560 GASOLINE COMPOSITIONS Warren L. Perilstein, Orchard Lake, Mich, assignor to Ethyl Corporation, Richmond, Va.

No Drawing. Continuation-impart of abandoned application Ser. No. 856,147, Sept. 8, 1969. This application Aug. 21, 1970, Ser. No. 66,122

Int. Cl. C101 1/06 U.S. CI. 44-80 49 Claims ABSTRACT OF THE DISCLOSURE Gasoline compositions containing normally liquid nonaromatic olefin hydrocarbons having an average molecular weight of from 350 to about 1500; the composition are characterized by substantially reducing the underhead intake valve deposit formation when used as fuels in a spark ignition, internal combustion engine. Preferred olefin hydrocarbons are those prepared by Friedel-Crafts polymerization of a mixture of monoolefins with carbon numbers ranging from about C and higher.

CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of Ser. No. 856,147, filed Sept. 8, 1969, now abandoned.

BACKGROUND OF THE INVENTION The present invention is concerned with gasoline compositions containing deposit reducing amounts of certain high molecular weight normally liquid olefin hydrocarbons; novel olefin hydrocarbons; and a method of preparing such olefin hydrocarbons.

During the operation of a spark ignition internal combustion engine, deposits are formed on portions of the intake system. The intake system is that part of the engine before the combustion chamber (cylinder) through which the air-fuel mixture is conducted. These deposits are appatently residues formed when the fuel and/or lubricant oil used in the engine contact the hot surfaces within the intake system. The deposits which form on the intake valve stem and the side opposite the valve face (underhead) are of special concern. Such deposits contribute to the intake valve failure by causing the valves to overheat for example; these deposits may also prevent proper seating of the intake valves which would result in engine malfunction. Thus, it is desirable that the formation of these deposits be minimized.

Gasoline additives which prevent or reduce engine deposits are disclosed in the art; see U.S. 1,692,784, U.S. 2,066,234, U.S. 2,080,681, U.S. 2,103,927 and U.S. 2,- 726,942. These additives are generally aromatic in nature; the alkylnaphthalenes are exemplary of such additives. One disadvantage of these known additives is that relatively high concentrations are required for good effectiveness.

It has been discovered that a relatively small amount of a non-aromatic olefin hydrocarbon is extremely effective as an additive in gasoline for preventing undesirable intake system deposits; and especially the aforesaid intake valve deposits.

SUMMARY OF THE INVENTION Gasoline containing an intake valve deposit reducing amount of a normally liquid, non-aromatic olefin hydrocarbon, having an average molecular weight ranging from 350 to about 1500, prepared by polymerizing a mixture of monoolefins containing about 12 or more carbon atoms; the olefin hydrocarbon per se; fluid concentrates containing normally liquid non-aromatic olefin hydrocarbon suitable for preparing the improved gasoline compositions.

3,749,560 Patented July 31, 1973 A preferred embodiment of this invention is gasoline containing an intake valve deposit reducing amount of a normally liquid non-aromatic olefin hydrocarbon having an average molecular weight ranging from 350. to about 1500, where the olefin hydrocarbon is prepared by polymerization of monoolefins having about 12 or more carbon atoms. More preferred olefin hydrocarbons are those obtained by polymerizing a mixture of even numbered, predominantly a, monoolefins having from 12 to about 32 carbon atoms using a Friedel-Crafts catalyst. Preferred Friedel-Crafts catalysts are aluminum chloride, aluminum bromide, and boron trifiuoride. Preferred temperatures are 20 C. C. A most prefererd polymerization process is carried out at temperatures ranging from about 40 C. to about 110 C., using an aluminum halide catalyst in the absence of any lower alkyl (C 0 monohalide. The improved gasoline compositions may also contain a tetraalkyllead antiknock agent and an organohalide scavenger.

The deposit reducing additives useful in the present invention are non-aromatic, normally liquid olefin hydrocarbons characterized by having an average molecular weight ranging from 350 to about 1500. By normally liquid is meant that the olefin hydrocarbon is fluid at room temperature. These olefin hydrocarbons include cyclic olefin hydrocarbons as well as branched chain and straight chain olefin hydrocarbons.

Although olefin hydrocarbons useful as additives may contain only one carbon number species, for example, triacontene (C pentacontene (C a C olefin and the like, preferred olefin hydrocarbons are mixtures of olefins having at least 16 or more and preferably at least 24 or more carbon atoms. The mixtures of olefins which make up these preferred olefin hydrocarbons may be obtained directly from commercial processes such as Ziegler catalyzed ethylene and/or propylene polymerization; dehydrohalogenation of suitable alkyl halides; the catalytic dehydrogenation of suitable parafiins, for example, wax cracked parafiins; or oligomerization of suitable olefins; or other similar processes.

Particularly preferred olefin hydrocarbon additives are those obtained by polymerizing non-aromatic, primarily a, monoolefin mixtures having 8 or more, and preferably 12 or more carbon atoms. By predominantly on is meant that more than 50% by weight of the monoolefin mixture have the or configuration.

The polymerization of these monoolefins can be elfected with various catalyst systems. Useful polymerization procedures are disclosed, for example, in U.S. 2,620,365, U.S. 3,206,523, U.S. 3,232,883, U.S. 3,252,771, U.S. 3,253,052, U.S. 3,259,668, U.S. 3,261,879, U.S. 3,322,848, U.S. 3,325,560, U.S. 3,330,883, U.S. 3,346,662, and U.S. 3,450,786. The olefin hydrocarbon products prepared using procedures such as those described in the patents listed may be useful as additives in the gasoline of the present invention provided that the product has the required average molecular weight, is normally liquid, and is non-aromatic in nature.

A most preferred normally liquid non-aromatic olefin hydrocarbon is the product obtained by polymerizing a mixture of even carbon numbered, predominantly on, monoolefins having from 12 to 32 carbon atoms using a Friedel-Crafts catalyst, preferably selected from aluminum chloride, aluminum bromide, and boron trifluoride, at reaction temperatures ranging from 0 C. to about C. A most preferred polymerization is carried out in the absence of any lower alkyl (C -C halide such as methylchloride, n-hexylchloride, isopropylchloride, ethylchloride and the like, at temperatures ranging from 20 C.ll C. AlCl and AlBr are most preferred catalysts.

The polymerization reaction is ordinarily carried out without the addition of any inert diluent. However, the polymerization can be carried out in the presence of an inert diluent, e.g., an alkane, if desired.

The polymerization reaction time is to a degree dependent on the monoolefin feed stream, the reaction temperature, the catalyst concentration and the like. For example, when aluminum chloride is used as the catalyst, at a reaction temperature of 70 C. with an olefin feed containing C C olefins, reaction times of 5 to 15 minutes can be sufficient. In general, reaction times can be varied as required by different reaction systems to prepare suitable olefin hydrocarbon polymers.

The preferred Friedel-Crafts catalysts are aluminum chloride, aluminum bromide, and boron trifiuoride. The concentration of catalyst used may be varied. Generally from about 2% to about of the catalyst based on the weight of monoolefin charged can be used. About 5% of the catalyst based on the weight of the olefin charged is conveniently used.

The monoolefins which can be polymerized using the Friedel-Crafts process described above are mixtures of acyclic monoolefins having from about 12 to about 32 carbon atoms. By olefins I mean olefin hydrocarbons. These monoolefin mixtures are synthesized by methods known in the art. For example, they may be prepared by cracking wax paraffins; by catalytically dehydrogenating parafiinic hydrocarbons; or by polymerizing low molecular weight monoolefins such as ethylene, using Ziegler-type catalysts. It is the general nature of these monoolefin preparations that mixtures of monoolefins are obtained. These monoolefins mixtures can vary widely in composition from 100% m-monoolefins, through intermediate mixtures, to 100% internal monoolefins; mixtures which contain 30% or more a-monoolefins are preferred. The range of carbon chain lengths in these mixtures can also vary considerably. Both branched and linear olefins can be present in these mixtures. Useful mixtures can also contain small amounts of monoolefins outside the C C range. Mixtures in which u-monoolefins predominate are more preferred; by predominate is meant that more than 50% by weight of the olefin mixture is a-monoolefin. In addition to the monoolefins, the mixture can also contain small quantities of certain lay-products (or co-product). The type of by-product or co-product found in the lit-monoolefin mixtures will depend to a great degree on the method used to prepare the monoolefins. Thus, for example, if the monoolefin mixture is prepared by catalytic dehydrogenation of parafiins in the C C range, the monoolefin mixture may contain some of the starting parafiin While with Ziegler catalyzed ethylene systems, the by-product present in the monoolefin may be parafiins as well as higher molecular weight alkanols. Generally, the monoolefin mixtures containing these by-products can be used as such; provided the presence of the by-product does not adversely afiect the Friedel- Crafts polymerization reaction and olefin hydrocarbon product.

Examples of useful monoolefin mixtures are those having the following monoolefin composition by weight: C12, C14: and C16; C13, C14, C15, C15, C17 and C; C9, C10, C11, C12, C13, C14 and C15, C12, C and C16; C3, cm, C12, C14, C15, C15, C20, C22 and 2% C24; C22 and C24; C25, C28 and C 5% C 15% C 30% C 32% C 10% C27 and C23; C16, C18, C20 and (322+; 6% C26, C23, C39, C32 and C34, and the like.

Preferred mixtures of monoolefins contain even carbon numbered olefins ranging from about C to about C with an tit-monoolefin content of 30% or more. These mixtures may contain small amounts of C C and C olefins as well as C or higher olefins; as well as paraffin and alkanol by-products as described above.

More preferred mixtures of monoolefins are those containing even carbon numbered olefins, ranging from about C to about C the olefins are predominantly a-monoolefins. These mixtures can also contain small amounts of C C and C olefins as well as C and higher olefins; as well as paratfin and alkanol by-products as described above.

Compositions of typical preferred monoolefin mixtures useful for Friedel-Crafts polymerization are listed in the following table. These preferred monoolefins will be designated herein as C monoolefins or (1 monoolefin mixtures.

Percent by weight 0 lefin carbon N 0.:

Gil C 1. 40 2. 01 4. 35 12 16. 72 19. 40 13. 92 Cr 9. '76 12. 59 9. 91 C16 8. 28 10. 97 9. 27 Cu; 6. 34 8. 88 9. 51 Czn =1. 43 5. L5 6. 04 C22 5. 59 6. 63 7. 51 Cm-.-" 7.50 7. 70 8.21 Cza 6. 41 4. 78 5. 80 C2! 3. 69 2. 40 3. 00 C20 1.25 0. 0. 61 C32 0. 38 0. 17

C31. 0. 08 Total olefins 70. 21 72 81. 58 78. 13 Total paraflins 18. 30 28 18. 42 21. 87 Other lay-products, percent 11. 49 Oltefin configuration, percent distribua 69. 7 60. 6 60. 9 Internal 30. 3 39. 3 39. l

Vapor phase chromatographic analysis.

1 Estimated.

Nuclear magnetic resonance analysis.

4 For this mixture, VPC analysis was based on 91.11% recovered normalized. The mixture also contained lay-product alcohols.

A typical mixture of C monoolefins has the following general composition by Weight; (I -C olefins3%, C C olefins39.2%, C olefins-33.6%, C C parafiins2%, C C paraffins19.4%, C paraffins0.8%, alcohols-2%.

A general composition range for another preferred monoolefin mixture comprises a mixture containing by C12, C14, C16, C13, 4-15% C 415% C 4-l6% C ()10% C 0-10% C 0-5% C 05% (3 the components being 60'- 90% olefins (30% or more a), 10-35% parafiins and 05% alcohols. This type of monoolefin mixture will be designated herein as a (1 monoolefin mixture.

Following is a table of useful C monoolefin mixtures.

TABLE 2.Ci4+ MONOOLEFIN MIXTURES 1 By produet paretfins and alkanols.

Another more preferred monoolefin mixture contains predominantly a-monoolefins of even carbon number ranging from C C Again, small amounts of olefins outside this range as well as by-products can also be present. These preferred monoolefin mixtures will be referred to herein as C monoolefins or C monoolefin mixtures. A general composition range of these C monoolefins is set out in the following table.

Table 3.C monoolefin composition range Olefin carbon No.: Percent by weight 1 C -6 C 0.5-22 C 32-55 C 18-39 C24 C 0.5-8 C 0-10 Paraffins 0-10 Olefin configuration percent distribution a: Vinyl 3055 Vinylidene 055 Internal -70 1 Vapor phase chromatographic (VPC) analysis.

2 C10- includes Cm and lower olefins; but essentially no olefins lower than about C12.

3 023 includes C23 and higher olefins.

* Nuclear magnetic resonance (NMR) analysis.

Specific examples of (3 monoolefin compositions are given in the following table.

TABLE 4.Crs MONOOLEFIN MIXTURES G H I J K L M N Percent by weight Olefin Carbon No.:

Cm 0.17 0.08 0.08 0.41 3.0 11 C1 9. 50 6.19 4.34 10. 83 16.7 63 C-" 47. 69 45.79 49.31 41.06 33.2 20 02 26.85 29.58 30.31 24.42 19.6 6 C21. 11.19 13.56 11.75 11.56 13.2 Czr- 13.54 4.13 2.97 4.16 6.3 C 0.87 0.66 0.91 0 94 7 9 C- 0. 19 0. 01 0.28 032 0.05 Parafiin h 5.07 3 Olefin configuration, percent distribution 2 Vinyl 50 8 .3 37.7 47.4 32.2 45 vinylidene- .5 46.7 32.2 37.3 3 45 Internal .4 15. 6 20.4 20.4 H 10 1 Vapor phase chromatographic analysis. 1 Nuclear magnetic reasonance anaylsis. 3 Estimated.

The more preferred monoolefin mixtures can also be treated with an isomerization catalyst prior to being polymerized. The isomerization efiected in this case is primarily isomerization of the vinylidene type u-olefins to internal olefins. Thus, for example, isomerizing a more preferred C olefin mixture containing 30% vinyl a-olefins, vinylidene rx-olefins, and 30% internal olefins using a suitable catalyst such as silica gel, activated alumina and the like, the isomerized C olefin will now contain 30% vinyl u-olefins, less than 40% vinylidene a-olefins and 30%+internal olefins, the indicating the amount of vinylidene olefin isomerized to internal olefin. Depending on the extent of vinylidene olefin isomerization, the resulting isomerized monoolefin mixture may contain (a) a-olefins predominantly, (b) internal olefins predominantly, or (c) an equal amount of a olefins and internal olefins. In any event, such isomerized olefin mixtures containing 30% or more a-monoolefins are also useful to prepare the olefin hydrocarbons of the present invention.

The following examples will illustrate the preparation of preferred olefin hydrocarbons by Friedel-Crafts polymerization of mixtures of a-monoolefins of the type disclosed above. All parts are by weight unless otherwise indicated. The molecular weight of the olefin hydrocarbon products was determined by vapor phase osmometry.

EXAMPLE 1 A vessel was charged with 383 parts of a C monoolefin mixture. To this olefin mixture was added 20 parts of aluminum chloride, gradually, over a 25-minute period. The vessel was cooled during the addition of the aluminum chloride in order to maintain the temperature of the reaction mixture at less than about 50 C. After the addition of the aluminum chloride was completed, the mixture was heated with stirring at C. for 2 hours. Then, about 1 00 parts of a 10% HCl solution was added to quench the catalyst. The reaction mixture was then diluted with hexane (to facilitate handling) and it was washed with water until the washings were free of acid. The reaction mixture was then filtered through Celite. Pat. 3,527,654 issued Sept. 8, 1970, by Jones and Brandon; The filtrate was stripped of water and solvent under vacuum on a steam bath. The product obtained was 320 parts of a clear yellow slightly viscous liquid. The infrared spectrum of this product indicated it to be a polymerized hydrocarbon. The molecular Weight was 818.

Similar results are obtained when aluminum bromide is used in Example 1 in place of the aluminum chloride. The reaction in Example 1 proceeds in an analogous manner when the reaction temperature is 0 C. and the reaction time is 12 hours; when the reaction temperature is 60 C. and the reaction time is 8 hours, or when the reaction time is increased to 3 hours.

EXAMPLE 2 A vessel was flushed with nitrogen and then charged with 454 parts of .a C L monoolefin mixture. The olefin mixture was cooled to 15 C.; 15 parts of aluminum chloride were added to this olefin mixture over a 3-4 minute period. The reaction mixture was then heated with stirring at 70 C. for 2 hours. The catalyst was then quenched by adding about parts of a 10 HCl solution to the mixture. About 350 parts of hexane were added (to facilitate handling) and the diluted mixture was washed with water until the washings were acid free. The reaction mixture was then filtered through Celite. The filtrate was stripped of water and solvent under vacuum on a steam bath. The product obtained was 308 parts of a clear, yellow, very fluid liquid. The molecular weight of this product Was 368.

An analogous product is obtained when the reaction of Example 2 is carried out at 0 C. for 16 hours; at 145 C. for 30 minutes; or at 40 C. for 5 hours. Boron trifiuoride is used with equal effectiveness in place of aluminum chloride in Example '2.

EXAMPLE 3 A vessel was charged with 589 parts of a C1z+ monoolefin mixture and 16.8 parts of aluminum chloride were added over a 6-minute period. The mixture was then heated with stirring at 110 C. for 3 hours, cooled, diluted with hexane and then it was treated with about 200 parts of a 10% HCl solution. The reaction mixture was then washed with water until the washings were free of acid and then it was filtered. The filtrate was stripped of water and solvent under vacuum to yield 509 parts of a clear, yellow, liquid product. The molecular weight of this product was 378.

A similar reaction is obtained when a C monoolefin mixture is used in place of the C L mixture in Example 3.

EXAMPLE 4 A mixture of 400 parts of a C monoolefin mixture and 400 parts of a C monoolefin mixture was charged to a flask and cooled to 20 C. This mixture of monoolefins was treated with 40 parts of aluminum chloride, added gradually over a 72-minute period. During the addition of aluminum chloride, the temperature was maintained at 21 C. The reaction was continued with stirring at 22 C.30 C. for 4 hours. The reaction mixture was then diluted with about parts of hexane and then it was treated with about 200 parts of a 10% HCl solution. The mixture was then washed with Water until acid free. It was filtered through Celite and the filtrate was stripped of solvent and water under vacuum. The product obtained was 696 parts of a clear, yellow liquid having a molecular weight of 623.

f A similar reaction is obtained when 80 parts of aluminum chloride are used in Example 4. At a reaction temperature of 120 C. analogous results are obtained after a 1 hour reaction period.

EXAMPLE A vessel was charged with 600 parts of a C monoolefin mixture. To this olefin mixture was added 17.1 parts of aluminum chloride, gradually, over a 35-minute period. The temperature during this addition ranged from 20-23" C. The reaction was continued with stirring at 23 C. for 3% hours. The mixture was then diluted with about 175 parts of hexane and it was treated with about 250 parts of a 1-101 solution. The mixture was then washed with water until acid free and it was then filtered through Celite. The filtrate was stripped under vacuum to yield 519 parts of a clear, yellow liquid product having a molecular weight of 366.

In another run, 877 parts of a predominantly or, C C range monoolefin mixture was polymerized using 75 parts of AlCl at 70 C. for 2 hours to produce a useful olefin hydrocarbon additive.

Analogous results are obtained in Example 5 when 12 parts of aluminum chloride, or 12 parts of aluminum bromide are used as the catalyst; or when the C monoolefin mixture is isomerized by contacting the mixture with silica gel for a short period of time.

EXAMPLE 6 The procedure of Example 5 is repeated except that a C monoolefin mixture is used and the reaction temperature is increased to 50 C. An analogous olefin hydrocarbon product is obtained, the molecular weight being somewhat higher than 366.

EXAMPLE 7 A 100 gallon glass-lined kettle is charged with about 500 pounds of a C monoolefin mixture. The olefin mixture is cooled to about 20 C. with agitation. About 25 pounds of aluminum chloride are then added to the agitated olefin mixture. The temperature of the mixture rises to about 95 C. after the AlCl addition. The mixture is cooled to about 50 C. A solution containing about 6.3 pounds 37% HCl and about 60.75 pounds of water is then added to the mixture and it is then heated to about 80 C. with agitation. When this temperature is reached, the agitation is discontinued and the mixture is allowed to stand for about minutes. Two layers form and the lower aqueous layer is separated and discarded. The remaining material constitutes the polymerized olefin hydrocarbon reaction product. This product is Washed twice with about gallons of water allowing about a 15-minute settling period for adequate phase separation after each wash. The water layer, after each wash, is separated and discarded. Finally, the washed reaction product is subjected to distillation under reduced pressure (about 40 mm; Hg). The distillate is a mixture of water and light hydrocarbons. This distillate is separated and the light hydrocarbon portion (which is part of the reaction product) is dried and is returned to the distilled product. The final product containing the light hydrocarbon is then cooled to room temperature and filtered. The yield of polymerized hydrocarbon olefin product is about 99.4% based on the C olefin charged. The product is an amber colored clear fluid having an average molecular weight of less than about 500.

Using substantially the procedure of Example 7, a series of polymerized olefin hydrocarbons was prepared. The (312 monoolefin mixtures used included those of the type listed in Table 1 or otherwise described above as Well as (1 monoolefin mixtures which were first isomerized, reducing their vinylidene olefin content. Properties of the polymerized olefin products thus obtained ranged as follows:

Physical appearance Amber fluid. Average molecular Weight 1 418464.

Flash point 2 2ll264 F. Viscosity at 20 C 38-49 cs.

Density at 20 C 0818-0820 g./ml.

' By osmometry.

2 Cleveland open cup.

The gasoline compositions of the present invention may contain the olefin hydrocarbon in a wide range of concentrations. The concentration of the olefin hydrocarbon may vary from 100 to 4000 parts per million (p.p.m.) by weight; preferred concentrations are from about 100 to 3500 p.p.m. More preferred gasoline compositions contain between about 400 and 2500 p.p.m. of olefin hydrocarbon. Most preferred gasoline compositions contain between about 1000 and 2500 p.p.m. of said olefin hydrocarbon.

In addition to the olefin hydrocarbon, the gasoline may also contain other gasoline additives provided these other additives do not adversely affect the present additive. Typical of such other'additives are antiknock compounds such as tetraalkylleads, cyclomatic metal compounds such as (methylcyclopentadienyl)manganese tricarbonyl, ferrocene; scavengers such as the alkylene halides; deposit modifiers such as tricresyl phosphate, cresyl diphenyl phos phate, promoters such as tert-butyl acetate; antioxidants such as phenylene diamines, certain phenols and phosphites; antiicers such as methanol, isopropanol; metal deactivators, dyes, corrosion inhibitors, and the like.

In preparing gasoline compositions of the present invention, any internal combustion engine gasoline base fuels may be used. Gasoline is generally a blend of hydrocarbons boiling from about 25 C. to about 225 C. which occur naturally in petroleum and suitable hydrocarbons made from petroleum by processes such as thermal or catalytic cracking, reforming and the like. Hydrocarbon compositions of typical base gasolines are tabulated below; percentages are by volume.

TABLE 5.BASE GASOLINES.

A B C D E F G H I K K Percentoi:

momatlcsnu 28.5 30.0 30.0 29.0 60 60 8O 38 16 Olefinlcs 3.0 3.0 4.0 3.0 10 20 2o 7 12 Saturates 68.15 67.0 66.0 68.0 50 10 55 72 In preparing the gasoline compositions used in the present invention the olefin hydrocarbon additives may be added directly to the gasoline or they can be added as additive concentrates. Conventional gasoline blending processes and apparatus can be used. Following are ex EXAMPLE 8 A gasoline composition was prepared by adding to Base Gasoline B 3.15 grams of lead per gallon as tetraethyllead, about 1.43 grams (0.5 theories) of ethylene dibromide scavenger per gallon, about 1.51 grams (1.0 theories) of ethylene dichloride scavenger per gallon, and 500 parts per million (p.p.m) of the olefin hydrocarbon product of Example 1.

EXAMPLE 9 A gasoline composition was prepared by adding to Base Gasoline A 3.15 grams of lead per gallon as tetraethyllead, about 1.43 grams (0.5 theories) of ethylene dibro- 9 mide scavenger per gallon, about 1.51 grams (1.0 theories) of ethylene dichloride scavenger per gallon, and 250 p.p.m. of the reaction product of Example 3.

EXAMPLE 10 A gasoline composition was prepared by adding to Base Gasoline C about 3.19 grams of lead per gallon as tetraethyllead, about 1.51 grams (1.0 theories) of ethylene dichloride scavenger, and about 1.43 grams (0.5 theories) of ethylene dibromide scavenger, and 400 p.p.m. of olefin hydrocarbon prepared by the process of Example 7.

EXAMPLE 11 A gasoline composition was prepared by adding to Base Gasoline D about 3.21 grams of lead per gallon as tetraethyllead, about 1.51 grams (1.0 theories) of ethylene dichloride scavenger, about 1.43 grams (0.5 theories) of ethylene dibromide scavenger, and 2000 p.p.m. of olefin hydrocarbon prepared by the process of Example 7.

EXAMPLE 12 EXAMPLE 13 A gasoline composition is prepared by adding to Base Gasoline D 4 grams of lead per gallon as tetraethyllead, and 1 theory of ethylene dichloride per gallon and 550 p.p.m. of the olefin hydrocarbon product of Example per gallon.

EXAMPLE 15 A series of gasoline compositions is prepared by adding 100 p.p.m., 300 p.p.m., 650 p.p.m., 800 p.p.m., 3500 p.p.m., and 4000 p.p.m. of the product of Example 6 to each of Base Gasolines A through K EXAMPLE 16 Another series of gasoline compositions is prepared by adding 1.0 gram of lead per gallon as a tetraethyllead,

about 0.45 gram of ethylene dibromide and about 0.48

gram of ethylene dichloride to each of the Example 15 compositions.

EXAMPLE 17 A series of gasoline compositions is prepared by adding to each of Base Gasolines A through I containing 2 grams of lead per gallon as redistributed tetraethyllead/tetramethyllead mixture about 1.1 theories of ethylene halide scavenger per gallon, 200 p.p.m., 400 p.p.m., and 700 p.p.m. of the olefin hydrocarbon of Example 2.

EXAMPLE 18 A gasoline composition is prepared by adding to Base Gasoline A 100 p.p.m. of an olefin hydrocarbon additive having an average molecular weight of 1500.

EXAMPLE 19 A gasoline composition is prepared by adding to Base Gasoline B 800 p.p.m. of an olefin hydrocarbon having an average molecular weight of 350.

10 EXAMPLE 20 A gasoline composition is prepared by adding to Base Gasoline K 300 p.p.m. of an olefin hydrocarbon having an average molecular weight of 800.

EXAMPLE 21 A gasoline composition is prepared by adding to Base Gasoline D 450 p.p.m. of an olefin hydrocarbon having an average molecular weight of 1000.

EXAMPLE 22 A series of gasoline compositions is prepared by adding 400 p.p.m. of each of (a) C hydrocarbon olefin, (b) C hydrocarbon olefin mixture, and (c) a mixture of 50% C hydrocarbon olefin/50% C hydrocarbon olefin in each of Base Gasolines A through K,.

EXAMPLE 23 Another series of gasoline compositions is prepared by adding about 3 grams of lead per gallon as a tetraalkyllead antiknock and 1.6 theories of organohalide scavenger to the compositions of Example 22.

EXAMPLE 24 A series of gasoline compositions is prepared by adding p.p.m., 400 p.p.m., 700 p.p.m., 1500 p.p.m., 2500 p.p.m., 300-0 p.p.m., 3500 p.p.m., and 4000 p.p.m. of olefin hydrocarbon prepared by the process of Example 7 to each of Base Gasolines A through K.

EXAMPLE 25 Another series of gasoline compositions is prepared by adding about 2 grams of lead per gallon as a tetraalkyllead and about 1.3 theories of organohalide scavenger to the composition of Example 24.

Examples 8 through 25 illustrate, but do not limit the gasoline compositions of the present invention. In other words, suitable gasoline compositions can be prepared using the olefin hydrocarbons disclosed herein in any gasoline in the proportions taught above.

As pointed out previously, the olefin hydrocarbon additives can conveniently be added to the base gasoline in the form of concentrates or fluids. These additive fluids would contain sufiicient olefin hydrocarbon additive and any other gasoline additive desired in the finished gasoline such as antiknock agents such as tetraethyllead, tetramethyllead, (methylcyclopentadienyl)manganese tricarbonyl; halohydrocarbon scavengers; phosphate deposit modifiers; dyes; antiicers and the like. The exact composition of such additive fluids is determined by the physical characteristics of the materials such as compatability, solubility, and the like, as well as the concentration desired in the finished gasoline.

The intake system deposit reducing effect of the addivites of the present invention was determined by testing in an engine. The test procedure involved running a standard 6-cylinder automobile engine on the gasoline fuel to be tested for a total of 60 hours on a severe intake 'valve deposit cycle. This cycle consisted ofrunning the engine for seconds at 2000 revolutions per minute (r.p.m.) followed by 40 seconds at 500 rpm. for a total of 60 hours. At the end of this 60 hour test run, the manifold and head assemblies of the engine were removed for inspection. The intake valves were removed, weighed and photographed. The valves were then cleaned to remove all the accumulated deposits and reweighed. The total deposit Weight was obtained by subtracting the weight of the valves after they had been cleaned from the weight of the valves with the accumulated deposits. in this way, a direct measure of the effect of an additive on intake valve deposit formation was obtained. In addition to this direct measurement, a cleanliness rating based on visual inspection of the intake system of the engine was also made. The rating was based on a visual observation of the carburetor throttle body, the intake riser, the hot TABLE 6.INTAKE VALVE DEPOSIT REDUCTION- Gil-HOUR TEST Amount of olefin hydro- Intake Reduction carbon valve 1 in Clean- Test Gasoline additive deposits deposits, liuess No. composition (p.p.m.) (grams) percent index 4 1 Base None 6.02 $.25

gasoline. 2; Example 8 500 O. 33 95 44 3 Example 9-..- 250 1. 62 73 45 1 Although Base Gasolines A and B are given separate designation they are different batches of the identical commercial gasoline fuel. The base gasoline contained substantially the same amount of the same tetraethylleadlorganohalide commercial antiknock fluid as in the compositions of Examples 8 and 9.

1 Underhead.

8 Average of four runs.

4 50=cloan.

As the data above clearly show the olefin hydrocarbon additives of the present invention significantly reduce the intake valve deposits in an internal combustion engine. These additives result in intake valve underhead deposit reductions ranging from 73% up to 95%. The Cleanliness Index data also indicates that the entire intake system of the engine is benefitted when the present additives are used in the gasoline.

A second series of engine tests was run utilizing the same procedure as set out above except that the total test run time was only 30 hours. Following is the data obtained for a series of such 30 hours engine tests.

TABLE 7.INTAKE VALVE DEPOSIT REDUCTION- 30-HOUR TEST 3 Base gasoline C and D are different batches of the some commercial gasoline fuel. The base gasoline contained substantially the same amount oi TEL antiknock fiuid as Examples and ll. compositions.

1 Underhead.

3 Additive C is a commercial intake system deposit reducing additive which appears to contain about 35% by weight oi low boiling petroeurn fraction diluent.

The data in Table 7 again illustrates the effectiveness of the olefin hydrocarbons of the present invention in reducing build-up of deposits on intake valves. Table 7 also includes data for a test run (Test 7) which utilizes a gasoline composition containing a commercial intake system deposit reducing additive, Additive C, at recommended use concentration (4000 p.p.m Comparing the intake valve deposit reducing effectiveness of the present olefin hydrocarbon with that of commercial Additive C it is clear that the present additive is at least as effective as, and on a p.p.m. basis possibly more eitective than, this commercial Additive C.

A third series of engine tests was conducted. The purpose of this series of tests was to show the effectiveness of the present olefin hydrocarbon additives in removing deposits which had accumulated on the intake valves. For this evaluation, the 30 hour test run described above was made with Baseline fuel (which is the Base Gasoline containing the lead antiknock fluid but no olefin hydrocarbon additive or other deposit reducing additive) to build up intake valve deposits. The intake valves with the accumulated deposits from the 30 hour run on the Baseline fuel were then removed from the engine, weighed, and

the engine was reassembled. The 30 hour test procedure was then repeated using the same Baseline fuel now containing the olefin hydrocarbon additive (or other deposit reducing additive); At the end of this clean up run, the intake valves were then removed and reweighed. The loss in intake valve weight after the second 30 hour test run was the measure of the clean up effectiveness of the olefin hydrocarbon additive (or other deposit reducing additive); and it is reported as Percent Intake Valve Clean Up. Data for a series of such clean up runs is presented in the following table.

TABLE 8.INTAKE VALVE DEPOSIT REMOVAL 1 Base Gasoline D containing the some amount of TEL antiknock fluid as Examples 11 and 12.

2 Average of two runs.

3 Additive G is a commeroialintalre system deposit reducing additive which appears to contain about 35% by weight of low boiling petroleum fraction diluent.

The data in Table 8 clearly shows the clean up eifectivencss of the present olefin hydrocarbon additives (Test Nos. 8 and 9); and again illustrates that the present additives are at least as eifective for clean up as a commercial additive, Additive C (Compare Test No. 10 with Test No. 9).

Comparable intake valve deposit reduction and removal are obtained when fuel compositions of the other examples (or any of the fuels containing the additives described herein) are used in an internal combustion engine.

Comparable intake valve deposit reduction is obtained when the fuel compositions of the other examples (or any of the fuels containing the additives described herein) are used in an internal combustion engine.

The present invention is embodied as described above, in gasoline compositions, novel gasoline additive concentrate-s, novel olefin hydrocarbon products, and a process for preparing the novel olefin hydrocarbon additives.

These embodiments have been fully and properly described above. The invention is limited only within the spirit and scope of the following claims.

What is claimed is:

1. A spark ignition, internal combustion engine gasoline fuel composition comprising a blend of hydrocarbons boiling in the gasoline boiling range containing an intake deposit reducing amount of a non-aromatic, normally liquid olefin hydrocarbon having an average molecular weight ranging from 350 to about 1500 wherein said olefin hydrocarbon is prepared by polymerization of mixtures of monoolefins having about 12 or more carbon atoms.

2. The gasoline composition of claim 1 wherein said polymerization is carried out using a FriedelsCrafts catalyst.

3. The gasoline composition of claim 2 wherein said Friedel-Crafts catalyst is selected from aluminum chloride, aluminum bromide and boron triiiuoride and said polymerization is carried out at temperatures ranging from 0 C. to about C.

4. The gasoline composition of claim 3 wherein said monoolefin mixture is a mixture containing 30% or more alpha monoolefins having from about 12 to about 32 carbon atoms.

5. The gasoline composition of claim 4 wherein said monoolefins are predominantly alpha.

6. The gasoline composition of claim 5 wherein said monoolefins are even carbon numbered.

'7. The gasoline composition of claim 4 wherein said catalyst is aluminum chloride and said reaction temperature is from about 20 C. to about 110 C.

8. The gasoline composition of claim wherein said catalyst is aluminum chloride and said reaction temperature is from about 20 C. to about 110 C.

9. The gasoline composition of claim 6 wherein said catalyst is aluminum chloride and said reaction temperature is from about 20 C. to about 110 C.

10. The gasoline composition of claim 1 wherein said deposit reducing amount is about 100 parts per million by weight to about 4000 parts per million by weight.

11. The gasoline composition of claim 1 wherein said deposit reducing amount is about 400 parts per million by weight to about 2500 parts per million by weight.

12. The gasoline composition of claim 2 wherein said deposit reducing amount is about 100 parts per million by weight to about 2500 parts per million by weight.

13. The gasoline composition of claim 3 wherein said deposit reducing amount is about 100 parts per million by weight to about 2500 parts per million by weight.

14. The gasoline composition of claim 4 wherein said deposit reducing amount is about 100 parts per million by weight to about 4000 parts per million by weight.

15. Th gasoline composition of claim 4 wherein said deposit reducing amount is about 100 parts per million by weight to about 2500 parts per million by weight.

16. The gasoline composition of claim 4 wherein said deposit reducing amount is about 400 parts per million by weight to about 2500 parts per million by weight.

17. The gasoline composition of claim 7 wherein said deposit reducing amount is about 100 parts per million by weight to about 2500 parts per million by weight.

18. The gasoline composition of claim 8 wherein said deposit reducing amount is about 100 parts per million by weight to about 2500 parts per million by weight.

19. The g soline composition of claim 1 wherein said deposit reducing amount is about 100 parts per million by weight to about 4000 parts per million by weight.

20. The gasoline composition of claim 1 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon numbered, predominantly tic-monoolefins having from 12 to about 32 carbon atoms using from 2% to 10% by weight based on the u-monoolefin, of a catalyst selected from aluminum chloride, aluminum bromide and boron trifiuoride, at reaction temperatures ranging from 0 C. to about 145 C.

21. The gasoline composition of claim 1 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon numbered monoolefins having from about 12 to about 32 carbon atoms where at least 30% of said monoolefins have the vinyl olefin configuration and the remainder have an internal olefin configuration using from 2% to 10% by weight based on the monoolefin of a catalyst selected from aluminum chloride, aluminum bromide, and boron trifluoride at reaction temperatures ranging from about 20 C. to about 110 C.

22. The gasoline composition of claim 1 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon number monoolefins having from about 12 to about 32 carbon atoms where at least 30% of said monoolefins have the vinyl-olefin configuration, at least 29% have the vinylidene-olefin configuration and the remainder have an internal olefin configuration, using from 2% to 10% by weight based on the monoolefin, of a catalyst selected from aluminum chloride, aluminum bromide and boron trifiuoride, at reaction temperatures ranging from about 20 C. to about 110 C.

23. The gasoline composition of claim 1 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon numbered, monoolefins ranging predominantly from C C wherein at least 30% of the monoolefins are of the vinyl, at least 30% are of the vinylidene, and the remainder are of the internal olefin, using from 2% to 10% by weight based on the mono- 14 olefin, of a catalyst selected from aluminum chloride, aluminum bromide and boron trifiuoride, at reaction temperatures of from 20 C. to C.

24. The gasoline composition of claim 1 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon numbered monoolefins ranging predominantly from C -C wherein at least 30% of the monoolefins are of the vinyl, at least 29% are of the vinylidene, and the remainder are of the internal olefin, using from 2% to 10% by weight based on the monoolefin, of a catalyst selected from aluminum chloride, alu-' minum bromide and boron trifluoride, at reaction temperatures of from 20 C. to 110 C. I

25. The gasoline composition of claim 20 wherein said catalyst is aluminum chloride, said reaction temperature ranges fromm 20 C.-l 10 C.

26. The gasoline composition of claim 21 wherein said catalyst is aluminum chloride, said reaction temperature ranges from 20-110 C.

27. The gasoline composition of claim 22 wherein said catalyst is aluminum chloride, said reaction temperature ranges from 20-110 C.

28. The gasoline composition of claim 24 wherein said catalyst is aluminum chloride, said reaction temperature ranges from 20-110 C.

29. The gasoline composition of claim 20 wherein said deposit reducing amount is from 400 parts per million by weight to 2500 parts per million by weight.

30. The gasoline composition of claim 21 wherein said deposit reducing amount is from 400 parts per million by weight to 2500 parts per million by weight.

31. The gasoline composition of claim 22 wherein said deposit reducing amount is from 400 parts per million by weight to 2500 parts per million by weight.

32. The gasoline composition of claim 26 wherein said deposit reducing amount is from 400 parts per million by weight to 2500 parts per million by weight.

33. The gasoline composition of claim 1 additionally containing from 0.5 to about 4 grams of lead per gallon as tetraalkyllead antiknock agent and from 0.5 to 1.6 theories of halohydrocarbon scavenger.

34. The gasoline composition of claim 1 wherein said average molecular weight ranges from 350 to about 500.

35. The gasoline composition of claim 7 wherein said average molecular weight ranges from 350 to about 500.

36. The gasoline composition of claim 20 wherein said average molecular weight ranges from 350 to about 500.

37. The gasoline composition of claim 21 wherein said average molecular weight ranges from 350 to about 500.

38. The gasoline composition of claim 25 wherein said average molecular weight ranges from 350 to about 500.

39. The gasoline composition of claim 26 wherein said average molecular weight ranges from 350 to about 500.

40. An additive concentrate suitable for addition to gasoline containing a non-aromatic, normally liquid olefin hydrocarbon having an average molecular weight ranging from 350 to about 1500 wherein said olefin hydrocarbon is prepared by polymerization of mixtures of monoolefins having about 12 or more carbon atoms.

41. The additive concentrate of claim 40 wherein said polymerization is carried out using a Friedel-Crafts catalyst.

42. The additive concentrate of claim 41 wherein said monoolefin mixture is a mixture containing 30% or more alpha monoolefins having from about 12 to about 32 carbon atoms and said polymerization is carried out using a catalyst selected from aluminum chloride, aluminum bromide, and boron trifluoride at reaction temperatures ranging from 0 C. to about C.

43. The additive concentrate of claim 42 wherein said catalyst is aluminum chloride and said reaction temperature is about 20 C. to about 110 C.

44. The additive concentrate of claim 40 wherein said olefin hydrocarbon is prepared by polymerizing a mix- 1 3 ture of even carbon numbered, predominantly a-monoolefins having from 12 to about 32 carbon atoms using from 2% to 10 by weight based on the oz-I1'101100l6fi11, of a catalyst selected from aluminum chloride, aluminum bromide and boron trifiuoride, at reaction temperatures ranging from C. to about 145 C.

45. The additive concentrate of claim 40 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon numbered monoolefins having from about 12 to about 32 carbon atoms where at least 30% of said monoolefins have the vinyl olefin configuration and the remainder have'an internal olefin configuration using from 2% to by weight based on the monoolefin of a catalyst selected from aluminum chloride, aluminum bromide, and boron trifiuoride at reaction temperatures ranging from about C. to about 110 C.

46. The additive concentrate of claim 40 wherein said olefin hydrocarbon is prepared by polymerizing a mixture of even carbon number monoolefins having from about 12 to about 32 carbon atoms where at least of. said monoolefins have the vinyl olefin configuration, at least 29% have the vinylidene olefin configuration and the remainder have an internal olefin configuration, using from 2% to 10% by weight based on the monoolefin, of

a catalyst selected from aluminum chloride, aluminum bromide and boron trifluoride,- at reaction temperatures ranging from about 20 C. to about 110 C.

47. The additive concentrate of claim wherein said average molecular weight ranges from 350 to about 500.

48, The additive concentrate of claim 42 wherein said average molecular weight ranges from 350 to about 500.

49. The additive concentrate of claim 44 wherein said average molecular weight ranges from 350 to about 500.

References Cited UNITED STATES PATENTS 3,475,369 10/1969 Blunt 44-80 3,502,451 3/1970 Moore et a1. 4458 3,558,737 1/1971 Saines 44-80 2,852,579 9/1958 Walkey 4480 3,252,771 5/1966 Clough et a1. 44--80 DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner US. Cl. X.R. 4469; 252386 

